CN102350325A - Preparation method of high-purity monodisperse silica-based chromatographic packing - Google Patents
Preparation method of high-purity monodisperse silica-based chromatographic packing Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-purity monodisperse silica-based chromatographic packing. According to the preparation method, a silicon powder is used as a silicon source, and under the catalysis of an ammoniacal liquor and an ammonia gas, a monodisperse high-purity nanometer silica hydrosol is firstly synthesized; monodisperse urea formaldehyde/silica composite microballoons are then prepared by the polymerization induced colloid aggregation (PICA) and heat treatment is carried out on the composite microballoons to finally obtain the porous silica-based chromatographic packing. The silica-based chromatographic packing prepared by the above method has the particle size of 2-10 microns, the specific surface area of 150-400m<2>/g, the average pore diameter of 10-20nm and the average pore volume of 0.4-0.6cm<3>/g. The silicon powder is used as the silicon source and the ammoniacal liquor and ammonia gas are used as catalysts, so as to avoid interfusion of impurities such as metal and the like and obtain the monodisperse and high mechanical strength porous silica, which is a good chromatographic packing.
Description
Technical field
The present invention relates to a kind of manufacturing approach of nontoxic, tasteless, pollution-free ultra tiny inorganic material, especially a kind of high-purity, single preparation method who disperses silica matrix chromatogram packing.
Background technology
Chromatogram is being brought into play more and more important effect as a kind of separation, analysis means efficiently in fields such as current production, scientific research, detection, monitoring.As " heart " that chromatographic isolation is analyzed, chromatographic column filler is the key that realizes that complex component effectively separates.Silica gel has that mechanical strength is good, the pore structure of easy control and specific area, chemical stability is good and the heat endurance advantages of higher, becomes present application chromatograph packing material material the most widely.Present chromatographic column filler preparation research both domestic and external is very ripe; But traditional silica gel column packing all contains a certain amount of foreign metal like sodium, calcium, iron and aluminium etc.; These impurity increase the silica gel surface-active; Cause the chromatographic isolation peak seriously to trail; And specific adsorption occurs and influence chromatographic separation performance, so the column packing of high-purity silica gel matrix is vital to the chromatogram compartment analysis.The whole dependence on import of high-performance chromatographic column filler that China uses at present, therefore, the preparation of high-purity silica gel chromatograph packing material and research have important significance for theories and actual application value.
The preparation of silica matrix filler mainly with three kinds of monocrystalline silica flour, silicate and organosiloxanes as presoma.The disclosed Ludox that is used for preparative chromatography with porous spherical silica gel has used NaOH and ammoniacal liquor as catalyst mostly." manufacturing approach of the non-property freezed Ludox " (publication number: CN86100503A) was disclosed on August 12nd, 1987 like Patent Office of the People's Republic of China.The document has been introduced 100 ~ 300 order monocrystalline silica flours at 65 ~ 100 ℃, under the catalytic action of alkali, makes the method for Ludox when optimal temperature is 72-83 ℃.Most domestic is introduced explained hereafter by the document basically with the enterprise of monocrystalline silica flour production Ludox at present.Patent CN1830778A is no more than 5% of alkaline aqueous solution total amount through the monocrystalline silica flour amount of controlling each adding, and the time interval is lower than under the condition of 60min, has synthesized the large grain size nanometer grade silicon dioxide colloid of particle diameter at 20 ~ 160nm.Aspect the preparation of the high-purity silicon dioxide hydrosol or silica gel, be the trade secret of patented technology or enterprise mostly, develop high-purity, single silica gel chromatograph packing material that disperses and realize finally that also the silica gel commercialization is to fill the domestic gaps.When Wang Shaoming etc. mention the domestic foreign ion of measuring in the high-purity silicasol in " preparation of high-purity silicasol ingredient standard substance " in " chemical analysis metering; 2006 (15): 5 "; The normal assay method that adopts GJB1083-1993 requires impurity content less than 100 μ g/g or 100 μ g/ml in the standard.MILSTD ML-S-12613B (MU) has stipulated the analytical method of silica in the silicon dioxide colloid.
Commodity chromatograph packing material such as silica gel, bonded silica gel, aluminium oxide, organic polymer microballoon (comprising ion exchange resin), porous carbon etc., its granularity is generally 3 ~ 10um etc., and theoretical post is imitated can reach 1 ~ 160,000 number of plates/rice.Wherein, because silica gel material has a series of advantages such as above-mentioned said mechanical strength is good, be to use chromatograph packing material material the most widely at present.Polymerisation induced coacervation of colloid method (PICA) is a kind of method for preparing Bio-sil of comparative maturity; It is that urea, formaldehyde and the silica hydrosol polymerization reaction take place that contains certain grain size (as several to tens nanometers) generate Lauxite silica complex microsphere under the acid medium condition; Polymer molecule serves as the bridge that connects the colloid molecule here, and complex microsphere obtains inorganic microsphere after removing organic matter through heating and calcining.The happy and auspicious Liu Xia of Jiang Sheng is in the report of " full porous spherical silica matrix efficient liquid phase chromatographic stuffing progress " in " Chinese science B collects: chemistry; 2009; 39 (8): 687-710 "; The preparation method of Bio-sil is divided into four types: pile up silica bead method (being PICA); Two phase process, spray drying process and biological capsule method.Because PICA method equipment is simple, easy to operate, principle is clear, and specification requirement is not harsh, and this method is all adopted in many research work.The prepared silicon dioxide microsphere of PICA method need not to carry out hierarchical processing, just can directly adorn post and be used for chromatographic isolation.
As " heart " that chromatographic isolation is analyzed, chromatographic column filler is vital for chromatographic isolation, is the key that realizes that complex component effectively separates.Traditional silica gel reversed-phase column filler as based on raw mineral materials all contains a certain amount of metal impurities iron and aluminium etc., and these impurity can cause the silica gel surface-active to increase, and the acidity of the remaining silicon hydroxyl of filling surface strengthens, silica gel surface thereby have negative electricity.Under common separation condition, alkaline amalyzing substances is because of protonated positively charged, and its chromatogram keeps existing normal hydrophobic effect, and ion exchange is arranged again; The latter makes the chromatographic peak of alkali compounds and chelate seriously trail.This has not only strengthened the development difficulty of this type of material HPLC method, and meeting impact analysis result's the degree of accuracy and reappearance.Therefore, high-purity silica matrix filler all is vital to the preparation and the compartment analysis of chromatographic column.The whole dependence on import of high-performance chromatographic column filler of present domestic use, therefore, this important function for of research has important theoretical and realistic meaning with deep to the production domesticization that realizes chromatograph packing material.
Summary of the invention
The purpose of this invention is to provide a kind of high-purity, single preparation method who disperses silica matrix chromatogram packing, can prepare micron-sized high-purity, the single dispersion and the high Bio-sil of mechanical strength.
High-purity, single preparation method who disperses silica matrix chromatogram packing, adopting the monocrystalline silica flour is the silicon source, with ammoniacal liquor and ammonia as catalyst, synthetic earlier single dispersion, the high-purity nano silicon hydrosol; Utilize polymerisation induced coacervation of colloid method (PICA) to prepare single dispersed urea aldehyde SiO 2 composite microsphere then, make the spherical silica gel chromatographic column filler through high-temperature roasting again.
Concrete preparation process is following:
A,, the reactor of reflux adds ammoniacal liquor in being housed; Open stirring when being warming up to 50-60 ℃; In 15-30ml ammoniacal liquor: the ratio of 1g silica flour adds silica flour; When continuing to be warming up to 70-80 ℃; Dropping ammonia keeps the pH value 11-12 of reactant liquor in reactor, after half an hour, feeds ammonia; Finish reaction after 4-6 hour, obtaining mass concentration is 8 ~ 20% silica hydrosols; Said ammoniacal liquor is analyzed pure ammoniacal liquor for concentration 25-28%, and the purity of said silica flour is greater than 99.9%, and particle diameter is the 60-80 micron;
B, in the silica hydrosol of steps A, add hydrochloric acid and regulate its pH=1 ~ 3; Again to wherein adding urea; Regulating mixeding liquid temperature is 10-15 ℃; Add formalin; Wherein the molar ratio of urea and formaldehyde is 1:1.3-1.9, and the gross mass of urea and formaldehyde and the mass ratio of silica are between 1:1-5; Stir 3-8min fast, left standstill 12-15 hour, cyclic washing obtains Lauxite/SiO 2 composite microsphere;
C, Lauxite/SiO 2 composite microsphere of step B is transferred in the reactor that is connected with division box; Ratio according to Lauxite/SiO 2 composite microsphere and deionized water is that 10-14g/100ml adds deionized water; Add and the isopyknic isoamyl acetate of deionized water again; When being warmed up to 95-97 ℃; Obvious layering can appear in the water knockout drum; The aqueous solution of lower floor is separated, continued to be warming up to and stop branch water more than 110 ℃; After filtering complex microsphere is placed vacuum drying chamber, in 110-120 ℃ of dry 10-15h, again in 180-200 ℃ of dry 20-25h; Slowly segmentation roasting, roasting 2-3 hour, obtains Bio-sil by 500-700 ℃ in Muffle furnace.Preferable heating schedule is: room temperature-200 ℃ heats up with 3-10 ℃ of/minute clock rate, and 200-300 ℃ heats up with 1-4 ℃ of/minute clock rate, and insulation 2-4 hour in the time of 300 ℃; 300-400 ℃ heats up with 3-10 ℃ of/minute clock rate, and 400-500 ℃ of 1-3 ℃ of/minute clock rate heats up, and 500 ℃ of insulations 3-5 hour; 500-700 ℃ heats up with 4-6 ℃ of/minute clock rate, and in the time of 700 ℃ 2-3 hour, obtain Bio-sil.
Bio-sil to obtaining characterizes, and the result is following
1, adopt the ICP-MS elementary analysis, wherein do not detect potassium, magnesium, iron, calcium, sodium content is 0.23 μ g/ml, meets in the assay method of GJB1083-1993 impurity content less than 100 μ g/g or the standard-required of 100 μ g/ml;
2, Fig. 1 is the stereoscan photograph of silica gel, from photo, can observe its particle diameter and be distributed in about 3um, is spherical-like morphology and distributes, and size has dispersed preferably more in the lump;
3, Fig. 2 is the BET analysis chart of silica gel, is 10nm by visible its average pore size of figure, and average pore volume is 0.47cm
3/ g, and to measure its specific area be 190m
2/ g;
4, Fig. 3 is the stereoscan photograph of silica gel, from photo, can observe its particle diameter and be distributed in about 3um, has demonstrated spherical-like morphology and homogeneous particle diameter distribution preferably, and better dispersed;
5, Fig. 4 is the chromatographic performance evaluation example of silica gel, is that p-nitrophenyl is the separation that thing carries out.Can see that from figure three chromatographic peak separating degrees and peak type are all relatively good, demonstrate its good separating property; Confirm its post effect about 30,000 number of plates/rice through reality dress post, dissymmetry factor is 0.95 ~ 1.09, and separating degree is more than 3.5.
The invention has the beneficial effects as follows:
1, the present invention replaces soluble silicate such as waterglass or positive silicate class as the silicon source with high-purity silicon powder, as catalyst, can avoid introducing metal impurities (like sodium, iron, aluminium etc.) or residual ester alcohol with aqueous ammonia to replace alkali metal effectively; The adding of ammonia has improved catalytic activity, the accelerated reaction process.
2, adopt the silica gel pore structure of method preparation of the present invention to be evenly distributed, monodispersity is good, purity is high, need not hierarchical processing and just can directly be used for chromatographic isolation.
3, this silica gel is used as chromatographic column filler, has mechanical strength height, advantage that separating power is strong, it is having very big potential using value aspect chromatographic isolation analysis.
Description of drawings
1, Fig. 1 is through the Electronic Speculum figure to the product of embodiment one;
2, Fig. 2 is through the BET figure to the product of embodiment two;
3, Fig. 3 is through the Electronic Speculum figure to the product of embodiment three;
4, Fig. 4 is through the chromatography figure to the product of embodiment three.
The specific embodiment
Embodiment one
A,, the 500ml there-necked flask of reflux adds 160ml ammoniacal liquor in being housed; Warming-in-water to 50 ℃ is opened stirring, adds the 16g silica flour; Continuing to be warming up to bath temperature reaches 80 ℃ and begins to be incubated timing; And with the speed of dripping 10ml half an hour 100ml ammoniacal liquor is added in the reaction vessel, being incubated after 2 hours, beginning feeds ammonia off and on; And keep the pH value of reactant liquor to be not less than 11; Finish reaction after 4 hours, recording its solid content is 15.31%, and reaction yield is 72.53%;
B, get above-mentioned make silica hydrosol 100g in there-necked flask; The concentration of using deionized water to regulate the hydrosol is 14%; Add 3.0g urea; And regulate mixed liquor with hydrochloric acid and make pH value 1 ~ 2; Add 5.8g formalin after regulating mixeding liquid temperature to 15 ℃; Arrest reaction is 12 hours behind the quick stirring 5min, and filtration, washing obtain Lauxite/SiO 2 composite microsphere; Wherein the mol ratio of urea and formaldehyde is 1:1.5, and Lauxite/silica hydrosol mass ratio is 1:3;
C, Lauxite/SiO 2 composite microsphere of step B is transferred in the there-necked flask that is connected with water knockout drum; Add the 150ml deionized water; And add isopyknic isoamyl acetate; Be warming up to and occur obvious layering in the water knockout drum; The aqueous solution of lower floor is separated, continued to be warming up to and stop branch water more than 110 ℃; After filtering complex microsphere is placed the vacuum drying chamber vacuum drying; 120 ℃ of dryings 12 hours and 200 ℃ of dryings 24 hours; Through the slowly roasting stage by stage in Muffle furnace of the resin balls after the vacuum drying; Be that room temperature-200 ℃ heating rate is 5 ℃/minute; 200-300 ℃ of heating rate is 2 ℃/minute, and insulation is 2 hours in the time of 300 ℃; 300-400 ℃ of heating rate is 5 ℃/minute, and 400-500 ℃ of heating rate is 2 ℃/minute, and 500 ℃ are incubated 2 hours; 500-700 ℃ of heating rate is 5 ℃/minute, and insulation is 2 hours in the time of 700 ℃; Naturally cool to room temperature, obtain the Bio-sil chromatograph packing material.
Embodiment two
A,, the 500ml there-necked flask of reflux adds 160ml ammoniacal liquor in being housed; Warming-in-water to 55 ℃; Open and stir adding 12g silica flour, continue to be incubated timing when the intensification bath temperature reaches 75 ℃, and 140ml ammoniacal liquor is added in the reaction vessel with the speed of dripping 10ml half an hour; Be incubated after 2 hours; Beginning feeds ammonia off and on, and finishes to react after keeping the pH value of reactant liquor to be not less than 11,6 hours; Recording its solid content is 12.31%, and reaction yield is 73.28%;
B, get above-mentioned make silica hydrosol 100g in there-necked flask; The concentration of using deionized water to regulate the hydrosol is 12%; Add 3.7g urea; And regulate mixed liquor with hydrochloric acid and make pH value 1 ~ 2; Add 6.4g formalin after regulating mixeding liquid temperature to 12 ℃; Arrest reaction is 12 hours behind the quick stirring 3min, and filtration, washing obtain Lauxite/SiO 2 composite microsphere; Wherein the mol ratio of urea and formaldehyde is 1:1.3, and Lauxite/silica hydrosol mass ratio is 1:2;
C, Lauxite/SiO 2 composite microsphere of step B is transferred in the there-necked flask that is connected with water knockout drum; Add the 120ml deionized water and add isopyknic isoamyl acetate; Be warming up to and occur obvious layering in the water knockout drum; The aqueous solution of lower floor is separated, continued to be warming up to and stop branch water more than 110 ℃; After filtering complex microsphere is placed the vacuum drying chamber vacuum drying; 120 ℃ of dryings 10 hours and 200 ℃ of dryings 22 hours; Resin balls after the vacuum drying is slowly roasting stage by stage in Muffle furnace; Be that room temperature-200 ℃ heating rate is 5 ℃/minute; 200-300 ℃ of heating rate is 2 ℃/minute, and insulation is 2 hours in the time of 300 ℃; 300-400 ℃ of heating rate is 5 ℃/minute, and 400-500 ℃ of heating rate is 2 ℃/minute, and 500 ℃ are incubated 2 hours; 500-700 ℃ of heating rate is 5 ℃/minute, and insulation is 2 hours in the time of 700 ℃; Naturally cool to room temperature, obtain the Bio-sil chromatograph packing material.
Embodiment three
A,, the 500ml there-necked flask of reflux adds 160ml ammoniacal liquor in being housed; Warming-in-water to 50 ℃; Open and stir and the 14g silica flour, continue to be warming up to bath temperature and reach 80 ℃ of insulation timing, with the speed of dripping 10ml half an hour 120ml ammoniacal liquor is added in the reaction vessel then; After being incubated about 2 hours; Beginning feeds ammonia off and on, and finishes to react after keeping the pH value of reactant liquor to be not less than 11,5 hours; Recording its solid content is 14.35%, and reaction yield is 72.63%;
B, get above-mentioned make silica hydrosol in there-necked flask; The concentration of using deionized water to regulate the hydrosol is 13%; Add 1.8g urea; And regulate mixed liquor with hydrochloric acid and make pH value 1 ~ 2; Add 4.6g formalin after regulating mixeding liquid temperature to 15 ℃; Arrest reaction is 12 hours behind the quick stirring 4min, and filtration, washing obtain Lauxite/SiO 2 composite microsphere; Wherein the mol ratio of urea and formaldehyde is 1:1.9, and Lauxite/silica hydrosol mass ratio is 1:4;
C, Lauxite/SiO 2 composite microsphere of step B is transferred in the there-necked flask that is connected with water knockout drum; Add the 140ml deionized water and add isopyknic isoamyl acetate; Be warming up to and occur obvious layering in the water knockout drum; The aqueous solution of lower floor is separated, continued to be warming up to and stop branch water more than 110 ℃; After filtering complex microsphere is placed the vacuum drying chamber vacuum drying; 120 ℃ of dryings 12 hours and 200 ℃ of dryings 24 hours; Resin balls after the vacuum drying is slowly roasting stage by stage in Muffle furnace; Be that room temperature-200 ℃ heating rate is 5 ℃/minute; 200-300 ℃ of heating rate is 2 ℃/minute, and insulation is 2 hours in the time of 300 ℃; 300-400 ℃ of heating rate is 5 ℃/minute, and 400-500 ℃ of heating rate is 2 ℃/minute, and 500 ℃ are incubated 2 hours; 500-700 ℃ of heating rate is 5 ℃/minute, and insulation is 2 hours in the time of 700 ℃; Naturally cool to room temperature, obtain the Bio-sil chromatograph packing material.
Claims (3)
1. high-purity, single preparation method who disperses silica matrix chromatogram packing, concrete preparation process is following:
A,, the reactor of reflux adds ammoniacal liquor in being housed; Open stirring when being warming up to 50-60 ℃; In 15-30ml ammoniacal liquor: the ratio of 1g silica flour adds silica flour; When continuing to be warming up to 70-80 ℃; Dropping ammonia keeps the pH value 11-12 of reactant liquor in reactor, after half an hour, feeds ammonia; Finish reaction after 4-6 hour, obtaining mass concentration is 8 ~ 20% silica hydrosols;
B, in the silica hydrosol of steps A, add hydrochloric acid and regulate its pH=1 ~ 3; Again to wherein adding urea; Regulating mixeding liquid temperature is 10-15 ℃; Add formalin; Wherein the molar ratio of urea and formaldehyde is 1:1.3-1.9, and the gross mass of urea and formaldehyde and the mass ratio of silica are between 1:1-5; Stir 3-8min fast, left standstill 12-15 hour, cyclic washing obtains Lauxite/SiO 2 composite microsphere;
C, Lauxite/SiO 2 composite microsphere of step B is transferred in the reactor that is connected with division box; Ratio according to Lauxite/SiO 2 composite microsphere and deionized water is that 10-14g/100ml adds deionized water; Add and the isopyknic isoamyl acetate of deionized water again; When being warmed up to 95-97 ℃; Obvious layering can appear in the water knockout drum; The aqueous solution of lower floor is separated, continued to be warming up to and stop branch water more than 110 ℃; After filtering complex microsphere is placed vacuum drying chamber, in 110-120 ℃ of dry 10-15h, again in 180-200 ℃ of dry 20-25h; Slowly segmentation roasting, roasting 2-3 hour, obtains Bio-sil by 500-700 ℃ in Muffle furnace.
2. high-purity, single preparation method who disperses silica matrix chromatogram packing according to claim 1; The heating schedule that it is characterized in that step C is: room temperature-200 ℃ heats up with 3-10 ℃ of/minute clock rate; 200-300 ℃ heats up with 1-4 ℃ of/minute clock rate, and insulation 2-4 hour in the time of 300 ℃; 300-400 ℃ heats up with 3-10 ℃ of/minute clock rate, and 400-500 ℃ of 1-3 ℃ of/minute clock rate heats up, and 500 ℃ of insulations 3-5 hour; 500-700 ℃ heats up with 4-6 ℃ of/minute clock rate, and in the time of 700 ℃ 2-3 hour, obtain Bio-sil.
3. high-purity, single preparation method who disperses silica matrix chromatogram packing according to claim 1 is characterized in that the said ammoniacal liquor of steps A analyzes pure ammoniacal liquor for concentration 25-28%, and the purity of said silica flour is greater than 99.9%, and particle diameter is the 60-80 micron.
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| CN102849749A (en) * | 2012-09-19 | 2013-01-02 | 复旦大学 | Mesoporous-macroporous multilevel ordered monodisperse micron sphere and preparation method thereof |
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| US11628381B2 (en) | 2012-09-17 | 2023-04-18 | W.R. Grace & Co. Conn. | Chromatography media and devices |
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| CN105801659B (en) * | 2014-12-30 | 2018-12-18 | 广西梧州制药（集团）股份有限公司 | Purposes of the monodisperse polymer silica gel in ginsenoside Re and Rd purification |
| CN105801655B (en) * | 2014-12-30 | 2018-12-18 | 广西梧州制药（集团）股份有限公司 | Purposes of the monodisperse polymer silica gel in Rg1, Re and Rb1 purification |
| CN105801659A (en) * | 2014-12-30 | 2016-07-27 | 广西梧州制药（集团）股份有限公司 | Application of monodisperse polymerized silica gel in purification of ginsenosides Re and Rd |
| CN110523400A (en) * | 2018-05-25 | 2019-12-03 | 中科院大连化学物理研究所淮安化工新材料研究中心 | Microemulsion method synthesized silicon rubber chromatograph packing material |
| CN110215896A (en) * | 2019-06-05 | 2019-09-10 | 南京亘闪生物科技有限公司 | A kind of lithium absorption resin of porous silicon ball support and preparation method thereof |
| CN113083217A (en) * | 2021-03-25 | 2021-07-09 | 苏州环亚欣智能科技有限公司 | Preparation method of magnetic silica gel microspheres with controllable high pore diameters |
| CN114409951A (en) * | 2021-12-31 | 2022-04-29 | 北京化工大学 | Monodisperse composite foaming agent, micro-cellular plastic and preparation method thereof |
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